Method of making furfuryl acrylate



This method of, preparingboiling point Patented Jan. 6, 1948 Chessie E.

Fisher,

Rehberg, Philadelphia, and Charles H. Ablngton, Pp, asslgnors to the United States of America, as represented by the Secretary of Agriculture No Drawing. Applies Serial N tion December 27,1943, 0. 515,798

.2 Claims. (ci.2so-345)' 7 under the (Granted April 30,

amended This application is made under the act of March 3, 1883, as amended by the act of April 30, 1928, and the invention herein described, if patented, may be manufactured and used by Government of the United States of governmental purposes without the payment to us of any royalty thereon.

This invention relates to new composition of matter.

An object of this invention is to provide a new polymerizable composition of matter together with processes for its preparation and polymerization.

Other objects will appear from the followin description.

We have found that furfuryl acrylate, which may be prepared by an alcoholysis reaction of methyl acrylate with furfuryl alcohol, is a valuable polymerizable compound.

The alcoholysis reaction is suitably carried out by heating furfuryl alcohol with an excess of methyl acrylate in the presence at an ester interand a polymerization inhibitor,

furfuryl acrylate, a

removing the methanol formed by distillation of its azeotrope with methyl acrylate, and then recovering the iurfuryl aorylate tillation." Aluminum alcoholates, such minum tertiary-butoxide, are effective for the reaction, and the alcohplates catalysts of other metals, such as sodium and potassium, also give good results. Aromatic amines and-phenols are examples of convenient 'furiuryl acryl'ates is illustrated by Example I 98 parts (by-weight) of furfuryl alcohol, 258 parts of methyl acrylate, 10 parts of para-phenylenediamine and parts of powdered aluminum tertiary-butoxide were mixed and heated on a water bath until solution was complete. solution was then heated on an oil bath for approximatey temperatureof approximatel fractionating column fitted with a condenser arranged for controlling reflux. The distillate was collected at such that the temperature of the vaporv at th of the column remained at or near the boiling point oi the methanol-methyl acrylate binary azeotrope (62 C.). When the methanol had methyl acrylate was distilled and the furfuryl acrylate was duced pressure. Purified furfuryl f 93 C. at 16 mm.

polymerizationinhibitors. U

' copolymers.

the following example:

act of 1928;

. be effected by fractional dis-, .f,

as alu- I with a variety such as acid. Since iurfuryl acrylate has a multiplicity of polymerizable double .itis capable of forming cross-linked polymers and a rate March 3, 1883, as 370 O. G. 757) cc. and a reof 1.4800. of the it has a density of 1.1125 g. per fractive index for the D line of sodium The yield was 131 parts, or 86 percent theoretical.

The procedure outlined in Example I canbe advantageously modified by removing methanol from the reaction mixture as an azeotrope with an aliphatic hydrocarbon of suitable boiling range, rather than as an azeotrope with methyl acrylate. This is the subject of a copending application for patent by Chessie E. Rehberg, Serial No. 515,799, filed December 2'1, 1943, now Patent Number 2,406,561, issued August 27, 1946. Also, furfuryl acrylate may methods. Any suitable esterification or interchange process may be used.

furfuryl acrylate is a mobile liquid which may be polymerized with heat, light, and/or catalysts. Characteristically, a catalyst such as a peroxide, an ozonide, oxygen or ozone is employed. The polymerization may in the presence or absence of a solvent or diluent, or the monomer may be emulsified and then polymerized. Preferably, polymerization is carried out at moderate temperatures, that colorless,

I is, about 50 to c.

-.'Furfuryl other esters of acrylic bonds in its molecule,

I! desired, so-called polymerization regulators, such as polychloro hydrocarbons and mercaptans, may be added to the monomer to aid in preventing or controlling cross-linkage.

Relatively small ate in other polymerizable monomers the alkyl acrylates and methacrylates, produce appreciable alterations in the properties of the polymers formed. Thus, 5 percent or less of furfuryl acrylate, when copolymerized with methyl acrylate, produces a polymer which is relatively insoluble in the common organic solvents and which is appreciably harder and tougher than the polymer of methyl acrylate.

The polymerization of furfuryl acrylate is illustrated by the following examples:

Example 11 24 hours the entire solution had set to a stiff, colincident curing, milling, and so forth, may be carorless, transparent gel which was relatively inried the polymer was obtained as a tough, elastic, Polymers of the type formed by turfuryi acryl- 1- transparent solid which was harder, tougher and ate might also be formed with the substituted less soluble than methyl acrylate polymers. furfuryl acrylates. For example, alkyl i'urfuryl Example I acrylates, dlalkyl furfuryl acrylates, and halogen-f A copolymer of furfuryl and methyl acrylates pattern f unsatura was prepared as in Example II, except that to the acrylab-e Stead a viscous. sirupy true solution. A film pre- 1. The process or preparing Iurfu The properties of the polymers obtained by of aluminum tertiarybut polymerization of furfuryl acrylate, with or withtion inhibitor 2O 2. The process of preparing iurl'uryl acrylate range of hardness, solubility, fusibility, elast city, which comprises heatm thetgroceis are Well known to those a polymerization Inhibitor distilling the meth- 1n e 31' The polymers of furfuryl acrylate, and especialmethyl acrylate out of ly its copolymers with other polymerizable comthen recovering the 1 pounds, are valuable for moldings, extrusions, residua coatings, and the like. The peculiar type and de- CHESSIE REHBERG. gree of unsaturation in the furfuryl radical makes CHARLES FISHER this acrylate particularly valuable for copolymerization with other monomers. Under certain poly- REFERENCES CITED merizing conditions, as for instance in Example II, cross-linkage may be obtained in the polymer 35 3 2; i g g ggigz are of record in the in a degree which is controllable Within wide limits. Under other conditions, as illustrated by UNITED STATES PATENTS Example III, the cross-linkage may be partially Number Name Date or entirely prevented. The polymer thus obtained 2 109 877 Barrett Mar 1 1938 probably contains the furfuryl radical intact and 40 2 29 7 Barrett s 1938 hence is unsaturated. This linear, unsaturated 2:281:613 wouhan May 5:1942 polymer may be vulcanized with sulfur or other 2319 576 Agnes May 18 1943 known vulcanizlng agents to produce an elastic, 2 332461 Muskat Oct. 1943 rubber-like product. Such vulcanization, and the 

